Peculiarities of the silica surface center structure in rigid dehydroxidation conditions

A model of molecular claster and nonempirical calculation schemes MP2/6‐31G*, MP4/6‐31G*, and MP2/DZVP2 were applied to study electronic and energy characteristics of the surface centers of different SiO₂ modifications in rigid dehydroxidation conditions. It was established that depending on an angle α = Si′O′Si″ (where O′ is an oxygen atom of the nearest to the surface layer), O* atom corresponding with two surface Si atoms, could (i) form a chemical bond with one of the Si′ or Si″‐centers (an asymmetric configuration, α > 118° ÷ 120°); or (ii) be common for these centers (a symmetric configuration, α < 118° ÷ 120°). It was also established that when α > 132° ÷ 133°, the basic state was triple and at α < 132° ÷ 133°, it was single. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Polyacrylate/silica hybrid materials: A step towards multifunctional properties

Organic/Inorganic hybrid systems present a promising alternative for the creation of high-performance materials due to their biphasic structure that imparts multifunctional properties. The sol-gel process which initiated with the synthesis of inorganic glasses has now become a synthetic route for organic-inorganic assemblies due to several advantages such as mild processing conditions and the freedom to play with the structures of precursors. This versatility of the low-temperature sol-gel process provides an opportunity to engineer both the phases resulting in a synergistic combination or entirely new set of properties fruitful for different applications. This review highlights the several pathways for synthesis of silica particles, the interfacial modification and the classification of hybrid materials based on the method of incorporation of an inorganic moiety in the organic matrix along with the structure-property relationship, and the characterization to develop a fundamental understanding of the process. The nature of bonding between the two different species greatly affects the hybrid nanostructure and thus, the bulk properties of the system. In particular, acrylate/silica system has been focused due to its distinctive properties such as transparency, gloss, and strength that find large-scale application in the field of coatings, plastics and rubbers.Abbreviations: °: Degree; °C: Degree Celsius; ¹H NMR: Proton nuclear magnetic resonance; A°: Angstrom; AHAS: N-(3-acryloxy-2-hydroxyl propyl)-3-amino-propyltriethoxysilane; AIBA: 2,2′-Azobis(2-methylpropionamidine) dihydrochloride; AIBN: 2,2′-Azobis(2-methylpropionitrile); Al: Aluminium; APDMES: Aminopropyldimethylethoxysilane; APTES: 3-Aminopropyltriethoxysilane; ATRP: Atom transfer radical polymerization; CERAMERS: Ceramically Modified Monomers; CTAB: Cetyltrimethylammonium bromide; DFMA: Dodecafluoroheptyl methacrylate; DMF: Dimethylformamide; DPSD: Diphenylsilanediol; FESEM: Field Emission Scanning Electron Microscope; FTIR: Fourier-transform infrared spectroscopy; GPTMS: 3-Glycidoxypropyltrimethoxysilane; HDTMS: Hexadecyltrimethoxysilane; HEMA: 2-Hydroxyethyl methacrylate; HLB: Hydrophilic-Lyophilic Balance; HMDS: Hexamethyldisilazane; HPC: Hydroxypropyl Cellulose; IPN: Interpenetrating Network; KPS: Potassium persulfate; LCST: Lower critical solution temperature; McPTMS: 3-Mercaptopropyltrimethoxysilane; MOI: 2-(methacryloyloxy)ethyl isocyanate; MPEGMA: Monomethoxy-capped poly(ethylene glycol) methacrylate; MPTMS: 3-methacryloxypropyltrimethoxysilane; MTC: 2-(methacryloyl) ethyltrimethylammonium chloride; MTES: Methyltriethoxysilane; MTMS: Methyltrimethoxysilane; NMP: Nitroxide-Mediated Polymerization; ORMOCERs: Organically Modified Ceramics; ORMOSILs: Organically Modified Silica; OTES: Octyltriethoxysilane; OTMS: Octadecyltrimethoxysilane; PAA: Poly(acrylic acid); PDMS: Polydimethylsiloxane; PEO-PPO-PEO: Poly (ethylene oxides)-b-poly (propylene oxides)-b-poly (ethylene oxides); PHPS: Perhydropolysilazane; PMMA: Poly(methyl methacrylate); POSS: Polyhedral Oligomeric Silsesquioxane; PTMO: Poly(tetramethylene oxide); PTMS: Phenyltrimethoxysilane; PTMS: Phenyltrimethoxysilane; PVP: Poly (vinylpyrrolidone); RAFT: Reversible addition- fragmentation chain transfer; Si: Silicon; Sn: Tin; Ta: Tantalum; TBN: 4-(triethoxysilyl)butyronitrile; TEM: Transmission Electron Microscopy; TEMED: N,N,N′,N′-tetramethylethylenediamine; TEOS: Tetraethoxysilane; Tg: Glass-Transition Temperature; THF: Tetrahydrofuran; Ti: Titanium; TMOS: Tetramethoxysilane; UV: Ultraviolet; VTES: Vinyltriethoxysilane; VTMS: Vinyltrimethoxysilane; Zr: Zirconium

• Highlights

• Advantages of hybrid systems over the conventional materials

• Discusses the fundamental aspects of sol-gel chemistry

• Focusses on a detailed classification of hybrid polymers

• Covers different synthetic strategies, properties, and applications in diverse fields

     

Structural analysis of water adsorbed in silica gel

The melting point, T _f of water in a pore decreases as the surface area to pore volume ratio of the pore decreases. Analysis of water absorbed in the pores of silica gels using differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS) shows that the thickness of the bound, non-freezing water layer adjacent to the pore surface increases as its temperature increases, but that it is independent of the surface silanol concentration, [Si_sOH]. In contrast, the thickness decreases as the cylindrical pore radius r _H decreases. Thus, the increase in the bound water thickness from 0.45 nm for gels with r _H =1.2 nm to 1.2 nm for gels with r _H =7.5 nm is due to the increase from –53°C to –7°C of the temperature (e.g., the melting point T _f ) at which the bound water thickness was measured, and not due to the increase in t _H or the decrease in [Si_sOH]. The T _f of bulk water measured in a DSC was –0.3°C. The boiling point T _v of bulk water measured in a DSC was 81.3°C. T _v increased to 94°C in 7.5 nm pores and to 109°C K in 1.2 nm pores.     

Stepwise gradient of buffer concentration for capillary electrochromatography of peptides on sulfonated naphthalimido-modified silyl silica gel

The advantage of using a stepwise gradient of buffer concentration in CEC was demonstrated with the mixed-mode stationary phase, 3-(4-sulfo-1,8-naphthalimido)propyl-modified silyl silica gel (SNAIP). Before the application of a stepwise gradient, the effect of buffer concentration on the separations of six peptides and tryptic digests was investigated. Bubble formation caused by Joule heating at currents up to 95 microA was successfully suppressed by using SNAIP column even without pressurization, which contributed to a stepwise gradient of buffer concentration. Utilizing the stepwise gradient improved and shortened the separation of six peptides as compared to the separation under an isocratic elution.     

无胺法合成高硅丝光沸石的表征

采用XRD、SEM、FT-IR、MAS NMR等表征手段, 对以氟离子为结构导向剂无胺法合成的高硅丝光沸石进行了表征. 结果表明: 高硅丝光沸石结构属立方晶系, 晶胞参数小于传统低硅丝光沸石, 但b、c值要比相近硅铝比非氟体系合成的丝光沸石样品的大; 样品形貌及粒径与其硅铝比有关, 表明晶化条件对产物形貌及粒径均有影响; 随硅铝比的增大, FT-IR光谱中450、544、1053 cm-1谱带向高频移动, 720 cm-1谱带强度减弱, 表明骨架中铝减少而硅增多; 采用含氟无胺体系合成高硅丝光沸石时基本上不会产生非骨架铝.     

Alternate multi-layered adsorption of macro-cations and -anions on the colloidal spheres. Influence of the deionization of the complexation mixtures with coexistence of the ion-exchange resins

The alternate multiple adsorption layers of macrocations and macroanions on the surfaces of colloidal spheres, in which the complexation mixtures are deionized with ion-exchange resins are studied with help of the electrophoretic light-scattering, dynamic light-scattering and transmitted electron-microscopy techniques. The results are compared with those without resins. Colloidal silica spheres (110 nm in diameter) and monodispersed polystyrene spheres (220 nm) are used as colloidal spheres. The macrocations used are poly (4-vinyl-N-n-butyl pyridinium bromide) and poly (allylamine hydrochloride). Sodium poly (styrene sulfonate) and sodium polyacrylate are used as macroanions. The macroion-colloid complexations are formed firmly when the complexation suspensions are deionized with the resins.     

Synthesis of Silica Aerogels: Influence of the Supercritical CO2 on the Sol-Gel Process

The synthesis of silica aerogels was modified by addition of supercritical CO₂ during the sol-gel process. It was shown, that CO₂ acts as a catalyst and accelerates the gelation significantly. This effect was studied under a multitude of experimental conditions. The influence of the precursor concentration, temperature and the nature of the catalysts and solvent on the gel formation in presence of CO₂ was studied. Several gels obtained by this method were dried and transparent silica aerogels were produced.     

Study on the coating of nano-scale SiO<Subscript>2</Subscript> film on the surface of nanocrystalline Mg-Al layered double hydroxides

Since the layered double hydroxides (abbreviatedas LDHs) were firstly reported to be used as precur-sors of new catalytic materials by S. Miyata[1] in 1971,their preparations, ion-exchanges with the balancinginterlayer anions, structure characteristics an…     

Effective intraparticle diffusion coefficients of CoCl2 in mesoporous functionalized silica adsorbents

The scope of this work is to determine the effective intraparticle diffusion coefficient of CoCl₂ over mesoporous functionalized silica. Silica is selected as a carrier of the functionalized groups for its rigid structure which excludes troublesome swelling, often found in polymeric adsorbents. 2-(2-pyridyl)ethyl-functionalized silica is selected as a promising affinity adsorbent for the reversible adsorption of CoCl₂. The adsorption kinetics is investigated with the Zero Length Column (ZLC) method. Initially, experiments were performed at different flow rates to eliminate the effect of external mass transfer. The effect of pore size (60 Å and 90 Å), particle size (40?10^?6 m–1000?10^?6 m) and initial CoCl₂ concentration (1 mol/m³–2.0 mol/m³) on the mass transfer was investigated. A model was developed to determine the pore diffusion coefficient of CoCl₂ by fitting the experimental data to the model. The pore diffusion coefficients determined for two different pore sizes of silica are D _p (60 Å) =1.95?10^?10 [m²/s] and D _p (90 Å) =5.8?10^?10 [m²/s]. The particle size and the initial CoCl₂ concentration do not have an influence on the value of diffusion coefficient. However, particle size has an influence on the diffusion time constant. In comparison with polymer adsorbents, silica based adsorbents have higher values of diffusion coefficients, as well as a more uniform and stable pore structure.     

STUDIES ON THE FORMATION OF BIMETALLIC Rh-CoCLUSTERS FROM MONOMETALLIC RHODIUM ANDCOBALT CLUSTERS

IntroductionFormorethanonedecade,catalyticchemistshavemadenotableachievementsindevelopingthepreparativeapproachestoheterogenizedmolecularcatalystsandhighlydispersedmetalcatalystsfromorganometalliccompoundsandclusters,throughtheexplorationinsurfaceorganome…